CA1146579A - Process for the preparation of n-monosubstituted carbamic acid esters - Google Patents
Process for the preparation of n-monosubstituted carbamic acid estersInfo
- Publication number
- CA1146579A CA1146579A CA000367769A CA367769A CA1146579A CA 1146579 A CA1146579 A CA 1146579A CA 000367769 A CA000367769 A CA 000367769A CA 367769 A CA367769 A CA 367769A CA 1146579 A CA1146579 A CA 1146579A
- Authority
- CA
- Canada
- Prior art keywords
- process according
- carbamic acid
- alcohol
- employed
- amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- -1 N-MONOSUBSTITUTED CARBAMIC ACID Chemical class 0.000 claims abstract description 25
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 35
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- LBKPGNUOUPTQKA-UHFFFAOYSA-N ethyl n-phenylcarbamate Chemical compound CCOC(=O)NC1=CC=CC=C1 LBKPGNUOUPTQKA-UHFFFAOYSA-N 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical group COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 150000004998 toluenediamines Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000005002 naphthylamines Chemical class 0.000 claims description 2
- YPNZTHVEMNUDND-UHFFFAOYSA-N octyl carbamate Chemical compound CCCCCCCCOC(N)=O YPNZTHVEMNUDND-UHFFFAOYSA-N 0.000 claims description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 9
- 235000019441 ethanol Nutrition 0.000 claims 7
- 230000003197 catalytic effect Effects 0.000 claims 3
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical class C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 claims 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000006184 cosolvent Substances 0.000 abstract description 6
- 229940112021 centrally acting muscle relaxants carbamic acid ester Drugs 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 13
- 229910021529 ammonia Inorganic materials 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000012970 tertiary amine catalyst Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 150000003142 primary aromatic amines Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical class CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- QIJIUJYANDSEKG-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N QIJIUJYANDSEKG-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- OZDFMZUKOBBNHM-UHFFFAOYSA-N 2-ethylhexyl carbamate Chemical compound CCCCC(CC)COC(N)=O OZDFMZUKOBBNHM-UHFFFAOYSA-N 0.000 description 1
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 1
- PFDJIMKTGBPMEC-UHFFFAOYSA-N 2-methylpropylcarbamic acid Chemical class CC(C)CNC(O)=O PFDJIMKTGBPMEC-UHFFFAOYSA-N 0.000 description 1
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical class NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 description 1
- WETBJXIDTZXCBL-UHFFFAOYSA-N 3,5-dimethylhexan-1-ol Chemical compound CC(C)CC(C)CCO WETBJXIDTZXCBL-UHFFFAOYSA-N 0.000 description 1
- BRKFICIVZVLBDF-UHFFFAOYSA-N 3,5-dimethylhexyl carbamate Chemical compound CC(C)CC(C)CCOC(N)=O BRKFICIVZVLBDF-UHFFFAOYSA-N 0.000 description 1
- OLCIOXGQTLVZQT-UHFFFAOYSA-N 3-methylbutyl carbamate Chemical compound CC(C)CCOC(N)=O OLCIOXGQTLVZQT-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- GXYWJGVTMATDST-UHFFFAOYSA-N CCN(C(O)=O)C1=CC=CC=C1.CCN(C(O)=O)C1=CC=CC=C1 Chemical compound CCN(C(O)=O)C1=CC=CC=C1.CCN(C(O)=O)C1=CC=CC=C1 GXYWJGVTMATDST-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- UIQWBVPFHHQZHH-UHFFFAOYSA-N OOOOOOOOOOOOOO Chemical compound OOOOOOOOOOOOOO UIQWBVPFHHQZHH-UHFFFAOYSA-N 0.000 description 1
- CQGRLHBOVUGVEA-UHFFFAOYSA-N OOOOOOOOOOOOOOO Chemical compound OOOOOOOOOOOOOOO CQGRLHBOVUGVEA-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ANWCICBGKAHUEY-UHFFFAOYSA-N decyl carbamate Chemical class CCCCCCCCCCOC(N)=O ANWCICBGKAHUEY-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- AXMPFOXRWZXZFA-UHFFFAOYSA-N heptyl carbamate Chemical compound CCCCCCCOC(N)=O AXMPFOXRWZXZFA-UHFFFAOYSA-N 0.000 description 1
- GUMWTWBEQCYCCX-UHFFFAOYSA-N hexan-3-yl carbamate Chemical compound CCCC(CC)OC(N)=O GUMWTWBEQCYCCX-UHFFFAOYSA-N 0.000 description 1
- ROASJEHPZNKHOF-UHFFFAOYSA-N hexyl carbamate Chemical compound CCCCCCOC(N)=O ROASJEHPZNKHOF-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 description 1
- ZDZVWJQUOACMTH-UHFFFAOYSA-N n-(phenylsulfamoyl)aniline Chemical class C=1C=CC=CC=1NS(=O)(=O)NC1=CC=CC=C1 ZDZVWJQUOACMTH-UHFFFAOYSA-N 0.000 description 1
- YNTOKMNHRPSGFU-UHFFFAOYSA-N n-Propyl carbamate Chemical compound CCCOC(N)=O YNTOKMNHRPSGFU-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FSSYNTJUYWSXFS-UHFFFAOYSA-N n-ethyl-4-[4-(ethylamino)phenyl]aniline Chemical class C1=CC(NCC)=CC=C1C1=CC=C(NCC)C=C1 FSSYNTJUYWSXFS-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- RTKOPWMESJYXBN-UHFFFAOYSA-N n-ethylsulfanylaniline Chemical class CCSNC1=CC=CC=C1 RTKOPWMESJYXBN-UHFFFAOYSA-N 0.000 description 1
- VEROKHIMKPVCIS-UHFFFAOYSA-N n-heptyl-n-methyldecan-1-amine Chemical compound CCCCCCCCCCN(C)CCCCCCC VEROKHIMKPVCIS-UHFFFAOYSA-N 0.000 description 1
- HFSTWSJZQDETOA-UHFFFAOYSA-N n-methyl-n-nonyldecan-1-amine Chemical compound CCCCCCCCCCN(C)CCCCCCCCC HFSTWSJZQDETOA-UHFFFAOYSA-N 0.000 description 1
- GYNAVKULVOETAD-UHFFFAOYSA-N n-phenoxyaniline Chemical class C=1C=CC=CC=1NOC1=CC=CC=C1 GYNAVKULVOETAD-UHFFFAOYSA-N 0.000 description 1
- NVSYANRBXPURRQ-UHFFFAOYSA-N naphthalen-1-ylmethanamine Chemical class C1=CC=C2C(CN)=CC=CC2=C1 NVSYANRBXPURRQ-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 1
- ITCNMBZZNCMZMS-UHFFFAOYSA-N nonyl carbamate Chemical compound CCCCCCCCCOC(N)=O ITCNMBZZNCMZMS-UHFFFAOYSA-N 0.000 description 1
- MYDQAEQZZKVJSL-UHFFFAOYSA-N pentyl carbamate Chemical compound CCCCCOC(N)=O MYDQAEQZZKVJSL-UHFFFAOYSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
PROCESS FOR THE PREPARATION OF N-MONOSUBSTITUTED CARBAMIC ACID ESTERS ABSTRACT OF THE DISCLOSURE A process for the preparation of N-monosubstituted carbamic acid esters by reacting an unsubstituted carbamic acid ester and an aromatic primary amine at a suitable pressure and reaction temperature in the presence of a monohydric aliphatic alcohol and preferably in the presence of a strongly basic tertiary amine as catalyst. Optionally an inert co-solvent in addition to the alcohol may be employed.
Description
~ 7 BACKGROUND OF THE INVENTION
_ United States Patent No. 3,161,676 describes a process for the preparation of a substituted alkyl urea by reacting a carbamic acid ester with a primary and sterically unhindered secondary aliphatic amines in the presence of a metal compound Lewis acid catalyst, such as cupric acetate.
There is no known prior art which describes the preparation of N-monosubstituted carbamic acid esters by reacting an unsubstituted carbamic acid ester and an aromatic primary amine in the presence of a monohydric aliphatic alcohol with or without the use of a tertiary amine catalyst.
Many important commercial applications have been developed for the carbamic acid ester products of this invention, for example, as agricultural chemicals and chemical intermediates which may be converted to the corresponding isocyanate and alcohol by thermal decom-position or other methods described in the prior art.
SUMMARY OF THE INVENTION
The present invention is based on the unexpected discovery that it is possible to produce, in high yield and high conversions of reactants, an N-substituted carbamate, such as ethylphenylcarbamate (ethyl N-phenyl-carbamate), by the reaction of an aromatic primary amine such as aniline with an unsubstituted carbamate such as ethyl carbamate at a temperature of from about 125C to 250C in the presence of a monohydric aliphatic alcohol and preferably in the presence of a tertiary amine catalyst.
While the alcohol employed may, among other things, function 5~5~
as a solvent to effect the reaction, a co-solvent in addition to the alcohol may alternatively be used in the process of the invention.
It is a primary object of this invention there-fore, to provide a novel process for the preparation of N-monosubstituted carbamates.
It is another object of this invention to provide a novel reaction system for the conversion of an unsub-stituted carbamic acid ester and an aromatic primary amine to N-monosubstituted carbamic acid esters, such as ethyl-phenylcarbamate.
These and other objects and advantages of this invention will become apparent from the description of the invention which follows, and from the claims.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with this invention an N-substituted carbamic acid ester is produced by reacting an unsubstituted carbamic acid ester of the general formula NH2CO2R wherein R is a straight or branched chain alkyl group containing from l to 10 carbon atoms, with a primary aromatic amine of the general formula R'(NH2)n wherein R' may be a substituted or unsubstituted aryl or aralkyl group con-taining one or more benzenoid rings, preferably not more than six, which may be fused or joined by single valency bonds, dixectly or through bridging groups which may be, for example, oxygen or sulfur or a methylene group at a temperature in the range of from about 125C to 250C in the presence of a monohydric aliphatic alcohol having from l to 10 carbon atoms and preferably in the presence of a tertiary amine catalyst. Alternatively an inert solvent ~65~3 in addition to the alcohol may be employed. The R and R' may also contain substituents which do not interfere with the reaction, such as alkoxy, sulfur, sulfoxide, sulfone, etc. radicals. n is an integer of 1 to 6.
The reaction between the unsubstituted carbamic acid ester and the aromatic primary amine may be carried out in any suitable reactor, such as an autoclave, which is generally equipped with a means for agitation, means for regulating temperature and pressure and means for removing by-product ammonia, and possibly alcohol vapor.
Although the order of addition of the reactants, alcohol and solvents and catalyst components, if any, may vary, a general procedure for carrying out the reaction is to charge the unsubstituted carbamic acid ester, primary aromatic amine, alcohol and, preferably, a strongly basic tertiary amine catalyst into the reaction vessel and then heat the mixture to the desired temperature at atmospheric pressure or higher pressures, if required. The reaction can be carried out batchwise, semicontinuous, or as a continuous process. The reaction products are recovered and treated by any conventional method, such as distil-lation or fractionation to effect separation of the N-monosubstituted carbamate from unreacted starting material, catalyst, solvent and by-products.
The unsubstituted carbamic acid esters employed as reactants in the process of the present invention conform to the general formula NH2C02R wherein R is a substituted or unsubstituted straight or branched chain alkyl group containing from 1 to 10 carbon atoms. Repre-sentative unsubstituted carbamic acid esters suitable for use in this invention include, for example, methyl carbamate, ethyl carbamate, normal and isobutylcarbamates, propyl carbamate, amyl carbamate, isoamyl carbamate, hexyl carbamate, octyl carbamate, 2-ethylhexyl carbamate, decyl carbamates, heptyl carbamate, nonyl carbamate,
_ United States Patent No. 3,161,676 describes a process for the preparation of a substituted alkyl urea by reacting a carbamic acid ester with a primary and sterically unhindered secondary aliphatic amines in the presence of a metal compound Lewis acid catalyst, such as cupric acetate.
There is no known prior art which describes the preparation of N-monosubstituted carbamic acid esters by reacting an unsubstituted carbamic acid ester and an aromatic primary amine in the presence of a monohydric aliphatic alcohol with or without the use of a tertiary amine catalyst.
Many important commercial applications have been developed for the carbamic acid ester products of this invention, for example, as agricultural chemicals and chemical intermediates which may be converted to the corresponding isocyanate and alcohol by thermal decom-position or other methods described in the prior art.
SUMMARY OF THE INVENTION
The present invention is based on the unexpected discovery that it is possible to produce, in high yield and high conversions of reactants, an N-substituted carbamate, such as ethylphenylcarbamate (ethyl N-phenyl-carbamate), by the reaction of an aromatic primary amine such as aniline with an unsubstituted carbamate such as ethyl carbamate at a temperature of from about 125C to 250C in the presence of a monohydric aliphatic alcohol and preferably in the presence of a tertiary amine catalyst.
While the alcohol employed may, among other things, function 5~5~
as a solvent to effect the reaction, a co-solvent in addition to the alcohol may alternatively be used in the process of the invention.
It is a primary object of this invention there-fore, to provide a novel process for the preparation of N-monosubstituted carbamates.
It is another object of this invention to provide a novel reaction system for the conversion of an unsub-stituted carbamic acid ester and an aromatic primary amine to N-monosubstituted carbamic acid esters, such as ethyl-phenylcarbamate.
These and other objects and advantages of this invention will become apparent from the description of the invention which follows, and from the claims.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with this invention an N-substituted carbamic acid ester is produced by reacting an unsubstituted carbamic acid ester of the general formula NH2CO2R wherein R is a straight or branched chain alkyl group containing from l to 10 carbon atoms, with a primary aromatic amine of the general formula R'(NH2)n wherein R' may be a substituted or unsubstituted aryl or aralkyl group con-taining one or more benzenoid rings, preferably not more than six, which may be fused or joined by single valency bonds, dixectly or through bridging groups which may be, for example, oxygen or sulfur or a methylene group at a temperature in the range of from about 125C to 250C in the presence of a monohydric aliphatic alcohol having from l to 10 carbon atoms and preferably in the presence of a tertiary amine catalyst. Alternatively an inert solvent ~65~3 in addition to the alcohol may be employed. The R and R' may also contain substituents which do not interfere with the reaction, such as alkoxy, sulfur, sulfoxide, sulfone, etc. radicals. n is an integer of 1 to 6.
The reaction between the unsubstituted carbamic acid ester and the aromatic primary amine may be carried out in any suitable reactor, such as an autoclave, which is generally equipped with a means for agitation, means for regulating temperature and pressure and means for removing by-product ammonia, and possibly alcohol vapor.
Although the order of addition of the reactants, alcohol and solvents and catalyst components, if any, may vary, a general procedure for carrying out the reaction is to charge the unsubstituted carbamic acid ester, primary aromatic amine, alcohol and, preferably, a strongly basic tertiary amine catalyst into the reaction vessel and then heat the mixture to the desired temperature at atmospheric pressure or higher pressures, if required. The reaction can be carried out batchwise, semicontinuous, or as a continuous process. The reaction products are recovered and treated by any conventional method, such as distil-lation or fractionation to effect separation of the N-monosubstituted carbamate from unreacted starting material, catalyst, solvent and by-products.
The unsubstituted carbamic acid esters employed as reactants in the process of the present invention conform to the general formula NH2C02R wherein R is a substituted or unsubstituted straight or branched chain alkyl group containing from 1 to 10 carbon atoms. Repre-sentative unsubstituted carbamic acid esters suitable for use in this invention include, for example, methyl carbamate, ethyl carbamate, normal and isobutylcarbamates, propyl carbamate, amyl carbamate, isoamyl carbamate, hexyl carbamate, octyl carbamate, 2-ethylhexyl carbamate, decyl carbamates, heptyl carbamate, nonyl carbamate,
2 ethyl-l-butyl carbamate, 3,5-dimethyl-1-hexyl carbamate, and the like. In general, the methyl and ethyl esters are more readily available and are, therefore, more preferred.
The aromatic primary amines employed as reactants in the process of the present invention conform to the general formula R'(NH2)n wherein R' is a substituted or unsubstituted aryl or aralkyl group containing one or more benzenoid rings, preferably not more than six, which may be fused or joined by single valency bonds directly or through bridging groups which may be, for example, oxygen or sulfur or a methylene group; n is 1 to 6.
Representative amines as hereinabove described include, for example, aniline, toluidines, naphthylamines, benzyl-amines~ xylidines, xylene diamines, naPhthalene diamines, toluene diamines, xylylyene diamines, anisidines, phenetidines, 3,3'-dimethyl-4,~'-diphenyldiamine, phenyl-enediamines, 2,4'- and 4,4'-methylenedianiline, sulfonyl-dianilines, dimethylbenzylamine, naphthalenemethylamines, dimethyl and diethylbenzidines, methyl and ethylthio-anilines, biphenylamines and diamines, phenoxyanilines, thiodianilines, and the like. The polyamine made by condensing aniline with formaldehyde and used,for example, in the preparation of polymeric isocyanates may also be employed. In general, aniline and the toluene diamines ~¢i579 are preferred.
The alcohols which are employed are monohydric aliphatic alcohols containing from 1 to 10 carbon atoms.
It is generally preferred that the alcohol employed correspond to the alkyl group of the reactant unsubstituted carbamic acid ester in order to prevent the preparation of mixed N-substituted carbamates. The alcohols, in addition to acting as the reaction solvent, substantially inhibit side reactions and are generally employed in a molar excess based on the amine or unsubstituted carbamic acid ester reactants, i.e., from about a molar ratio of .5:1 to 15:1 of alcohol to amine or carbamate reactant employed to produce the N-substituted carbamic acid esters.
Representative alcohols which may be employed in the process of this invention include, for example, methanol, ethanol, n-propanol, n- and iso-butyl alcohols, amyl alcohol, hexanol, heptanol, octanol, nonanol, decanol, 2-ethyl hexanol, 2-methyl pentanol, 2-ethyl-1-butanol,
The aromatic primary amines employed as reactants in the process of the present invention conform to the general formula R'(NH2)n wherein R' is a substituted or unsubstituted aryl or aralkyl group containing one or more benzenoid rings, preferably not more than six, which may be fused or joined by single valency bonds directly or through bridging groups which may be, for example, oxygen or sulfur or a methylene group; n is 1 to 6.
Representative amines as hereinabove described include, for example, aniline, toluidines, naphthylamines, benzyl-amines~ xylidines, xylene diamines, naPhthalene diamines, toluene diamines, xylylyene diamines, anisidines, phenetidines, 3,3'-dimethyl-4,~'-diphenyldiamine, phenyl-enediamines, 2,4'- and 4,4'-methylenedianiline, sulfonyl-dianilines, dimethylbenzylamine, naphthalenemethylamines, dimethyl and diethylbenzidines, methyl and ethylthio-anilines, biphenylamines and diamines, phenoxyanilines, thiodianilines, and the like. The polyamine made by condensing aniline with formaldehyde and used,for example, in the preparation of polymeric isocyanates may also be employed. In general, aniline and the toluene diamines ~¢i579 are preferred.
The alcohols which are employed are monohydric aliphatic alcohols containing from 1 to 10 carbon atoms.
It is generally preferred that the alcohol employed correspond to the alkyl group of the reactant unsubstituted carbamic acid ester in order to prevent the preparation of mixed N-substituted carbamates. The alcohols, in addition to acting as the reaction solvent, substantially inhibit side reactions and are generally employed in a molar excess based on the amine or unsubstituted carbamic acid ester reactants, i.e., from about a molar ratio of .5:1 to 15:1 of alcohol to amine or carbamate reactant employed to produce the N-substituted carbamic acid esters.
Representative alcohols which may be employed in the process of this invention include, for example, methanol, ethanol, n-propanol, n- and iso-butyl alcohols, amyl alcohol, hexanol, heptanol, octanol, nonanol, decanol, 2-ethyl hexanol, 2-methyl pentanol, 2-ethyl-1-butanol,
3,5-dimethyl-1-hexanol, and the like. The lower aliphatic alcohols having 1 to 4 carbon atoms are preferred.
A general postulated equation for the reaction of the present invention may be represented as follows:
(catalyst) NH2CO2R + R'(NH2)n heat~
Unsubstituted Aromatic Carbamate primary amine n = 1 to 6 R'(NHC-OR)n + NH3 o Ammonia N-Substituted Carbamate i579 wherein R and R' are as hereinabove described. A wide variety of N-substituted carbamates can be prepared by the process of this invention.
Although an optional feature of this invention, it has also been discovered that improved yields and increased reaction rates can be obtained when the above reaction is carried out in the presence of a strongly basic tertiary amine catalyst. The tertiary amine catalysts may be an aliphatic, cycloaliphatic, arali-phatic or aromatic amine containing from 1 to 18 carbon atoms, which may be interrupted by oxygen, sulfur, nitrogen, sulfoxide or carbonyl substituents. In general, the amine employed as catalyst should be easily separated from reaction product and by-products. Representative amines suitable for use in the process of the invention include, for example, the trialkylamines such as the trimethyl, triethyl, tripropyl, tributyl, trihexyl, trioctyl, tridecyl, tridodecyl, etc. amines, triphenyl-amine, n-dodecyldimethylamine, n-tetradecyldimethylamine, n-hexyldecyldimethylamine, n-octyldecyldimethylamine, N,N,N',N'-tetramethylethylenediamine, N,N-dioctyl-l-octylamine, 1,4-diazabicyclo[2.2.2]octane, 4(N,N-dimethyl-amino) pyridine, pyridine, 1,5-diazabicyclo[3.4.0]non-5-ene, 1,8-diazabicyclo[5.4.0]-undec-7-ene, 1,1,3,3-tetramethyl-butylamine, methyldiethylamine, butyldimethylamine, benzyldimethylamine, and the like. The amount of tertiary amine catalyst which can be used in the process will generally range between about .01 to 30 mole percent, preferably .1 to 20 mole percent based on the aromatic primary amine employed in the reaction, but greater or ~65'~9 lesser quantities may be used if desired.
Although the process of the invention is preferably carried out using the monohydric aliphatic alcohol as the reaction solvent, other solvents or mixtures of solvents which are stable and substantially chemically inert to the components of the reaction system may be employed as a co-solvent in the reaction system if desired. Suitable co-solvents which may be employed, and generally in amounts of from 0 to 50 weight percent based on the reaction mixture, include, for example, benzene, toluenes, xylenes, dichlorobenzene, tetrahydrofuran, 1,2-dimethoxyethane, diphenylether, nitrobenzene, diethyleneglycol dimethyl ether, triethylene-glycol dimethyl ether, dimethylsulfoxide, and the like.
The ratio of reactants, i.e., unsubstituted carbamic acid ester and aromatic primary amine may be varied over any convenient range. The mole ratio of amine to unsubstituted carbamate may be between about 10:1 to 0.1:1 and is preferably between about 5:1 to 0.25:1.
The reaction of the present invention will proceed at temperatures of from about 125C to 250C.
It is generally preferred to operate the process at temperatures of from about 175C to 225C to obtain a convenient rate of reaction. The reaction temperature will depend on the particular N-substituted carbamic acid ester being produced and should be below the temperature at which significant decomposition of the product ester might occur.
The process of the present invention is generally carried out at atmospheric pressure, although higher S~79 pressures of up to 50 atmospheres may be used and especially at the higher reaction temperatures or when the reaction temperature is above the boiling point of the alcohol and/or reactant amine. Subatmospheric pressures may be employed, if desired.
Ammonia resulting from the reaction must be removed during the course of the reaction, otherwise reduced yields of product carbamate are obtained. When the reaction is carried out at one atmosphere the ammonia is simply allowed to escape from the reaction vessel. In reactions where elevated pressures are employed provisions must be made to remove ammonia. A simple, convenient method is to strip the ammonia from the reactor with a dry inert gas, such as nitrogen or carbon dioxide and/or with the resulting alcohol vapor provided the alcohol employed is volatile at the reaction temperature. When the alcohol vapor is used to strip or aid in stripping the ammonia from the reactor, additional or makeup alcohol can be added to the reactor at a rate to compensate for the vapor loss.
The reaction time is generally dependent on the N-monosubstituted carbamate being produced, the reaction temperature and the catalyst employed, if any, and will vary depending on whether the process if continuous or batch but will generally range between about one to several hours.
The following Examples are provided to illustrate the invention in accordance with the principles of this invention, but are not to be construed as limiting the invention in any way except as indicated by the appended s~9 claims.
In the Examples which follow, the reactions were run in a 300 ml stainless steel stirred autoclave. The amine, unsubstituted carbamic acid ester and alcohol, along with tertiary amine catalyst and co-solvent, if any, are charged to the reactor which is then flushed with nitrogen and the reactor heated to the desired reaction temperature for a specified time period. During the reaction vaporized alcohol and product ammonia are stripped from the reactor with or without the aid of an inert gas. Makeup alcohol is pumped into the reactor at a rate closely approximating the alcohol removed. At the end of the reaction time, the autoclave is cooled to ambient temperature and the contents combined with the stripped alcohol which was collected in a dry ice cooled trap and the total mixture analyzed by liquid chromatog-raphy (LC) for conversion of amine and unsubstituted carbamic acid ester and selectivities to N-monosubstituted carbamate. Amine and the unsubstituted carbamate conver-sions were calculated on the basis of moles of the amine and carbamate consumed by the reaction. Product selec-tivities were based on the moles of amine or unsubstituted carbamate consumed in preparing the N-monosubstituted carbamate and by-products.
Example 1 _ 23.3 g aniline, 22.2 g ethyl carbamate and 220 ml of dry ethanol (200 proof) was charged to the autoclave which was flushed several times with nitrogen and heated to 200C for a period of 3 hours. During the reaction period ethanol and ammonia were stripped from the reactor 10 .
5'79 with nitrogen at an average of 1.7 ml of ethanol per minute. The ethanol vapor containing ammonia and a small amount of aniline was condensed in a dry ice cooled trap. Makeup ethanol was pumped into the autoclave at a rate closely approximating the amount stripped. After the reaction period, the autoclave was cooled and the contents along with the ethanol condensate analyzed.
LC analysis showed an aniline conversion of 34 percent and an ethylcarbamate conversion of 47.2 pe~cent with selectivities to ethylphenylcarbamate of 79 mole percent and 47.2 mole percent based on aniline and ethylcarbamateS
respectively.
Example 2 . . _ .
Example 1 was repeated using 100 ml ethanol and 100 ml benzene co-solvent. Analysis of the product and ethanol condensate showed an aniline conversion of 54 percent and an ethylcarbamate conversion of 65 percent.
Selectivities to ethylphenylcarbamate was 75 mole percent and 62 mole percent based on aniline and ethylcarbamate, respectively.
Example 3 Example 1 was repeated using 0.76 g 1,8-diaza-bicyclo[5.4.0]undec-7-ene as catalyst. Analysis showed an aniline conversion o~ 62.4 percent and an-ethyl-carbamate conversion of 84 percent with selectivities to ethylphenylcarbamate of 96.5 mole percent and 71 percent based on aniline and ethylcarbamate, respectively.
Example 4 Example 2 was repeated using 100 ml diphenyl-ether as a co-solvent, along with 0.4 mole of pyridine as 1~i579 catalyst. Analysis showed an aniline conversion of 55 percent and an ethylcarbamate of 66 percent with selec-tivities to ethylphenylcarbamate based on aniline and ethylcarbamate of 92 and 86 mole percent, respectively.
Examples 5 to 23 In Examples 5 to 23, which follow in Table form, the general procedure as hereinabove described was repeated using various amines, unsubstituted carbamic acid esters, alcohols, tertiary amine catalysts and conditions as shown in Table 1. The results are set forth in Table 2.
3o '~1 .~
oooooo ooooooooo o oU~o U~ooooo ooooooooo o o~
~1 ~ ~ N ~ ~ N ~ \I ~ N ~ ~ r-l N
~ g $ ~ o o o ~ ~ o o ~ o o U~
~} I I
t:4 00 a~ t` ~ r-i 00 ~ r` ~' 00 r-- 1` N Ir) 0 1-- 0 0 ~ ~ ~ ~ ~ ~ ~ 1 ~ ~ ~ ~ O ~ ~ ~ ~ ~
8 ~ ~ ~ 8 ~ ~ O ~ ~
U~
~ ~$ $$$$$$ $$$$$$$ $~ $~ ~ $$$
,~ ~
U~ C~ ~ U t~ V ~ V ~ U V C~
~ o~ ~ ~
...... ........ ~.~;........ .
1~46S~9 , ~
o o ~r ~
ui ~r a Y
13a .
'~
~ 5 u~ o ~ o ~ In o ~
~ ~ ~D ~ ~ ~ ~ ~0 ~ ~ a~ ~ ~ co 1` ~ ~` ~ ~D
~ ~ ~ a) ~ & ~ ~
N
~ o o~ ~ I~ ~ ~ In ~ ~ ~ ~ I` oo u~ I~ o o U~ u~
U.5 ~D ~ co ~ a~ ~ ~ ~ ~ ~ ~ ~ ~ co oo a~ ~ a~ co ~U ~ U ~ U ~ U ~U ~U ~ U
',~
~.~
U~
g) o ~ o ~ co ~ o :~
a) 14 .
1~46S79 U ~ ~
~ ~ 3 ~
o , , ~ ,` CO ~ o 14a.
A general postulated equation for the reaction of the present invention may be represented as follows:
(catalyst) NH2CO2R + R'(NH2)n heat~
Unsubstituted Aromatic Carbamate primary amine n = 1 to 6 R'(NHC-OR)n + NH3 o Ammonia N-Substituted Carbamate i579 wherein R and R' are as hereinabove described. A wide variety of N-substituted carbamates can be prepared by the process of this invention.
Although an optional feature of this invention, it has also been discovered that improved yields and increased reaction rates can be obtained when the above reaction is carried out in the presence of a strongly basic tertiary amine catalyst. The tertiary amine catalysts may be an aliphatic, cycloaliphatic, arali-phatic or aromatic amine containing from 1 to 18 carbon atoms, which may be interrupted by oxygen, sulfur, nitrogen, sulfoxide or carbonyl substituents. In general, the amine employed as catalyst should be easily separated from reaction product and by-products. Representative amines suitable for use in the process of the invention include, for example, the trialkylamines such as the trimethyl, triethyl, tripropyl, tributyl, trihexyl, trioctyl, tridecyl, tridodecyl, etc. amines, triphenyl-amine, n-dodecyldimethylamine, n-tetradecyldimethylamine, n-hexyldecyldimethylamine, n-octyldecyldimethylamine, N,N,N',N'-tetramethylethylenediamine, N,N-dioctyl-l-octylamine, 1,4-diazabicyclo[2.2.2]octane, 4(N,N-dimethyl-amino) pyridine, pyridine, 1,5-diazabicyclo[3.4.0]non-5-ene, 1,8-diazabicyclo[5.4.0]-undec-7-ene, 1,1,3,3-tetramethyl-butylamine, methyldiethylamine, butyldimethylamine, benzyldimethylamine, and the like. The amount of tertiary amine catalyst which can be used in the process will generally range between about .01 to 30 mole percent, preferably .1 to 20 mole percent based on the aromatic primary amine employed in the reaction, but greater or ~65'~9 lesser quantities may be used if desired.
Although the process of the invention is preferably carried out using the monohydric aliphatic alcohol as the reaction solvent, other solvents or mixtures of solvents which are stable and substantially chemically inert to the components of the reaction system may be employed as a co-solvent in the reaction system if desired. Suitable co-solvents which may be employed, and generally in amounts of from 0 to 50 weight percent based on the reaction mixture, include, for example, benzene, toluenes, xylenes, dichlorobenzene, tetrahydrofuran, 1,2-dimethoxyethane, diphenylether, nitrobenzene, diethyleneglycol dimethyl ether, triethylene-glycol dimethyl ether, dimethylsulfoxide, and the like.
The ratio of reactants, i.e., unsubstituted carbamic acid ester and aromatic primary amine may be varied over any convenient range. The mole ratio of amine to unsubstituted carbamate may be between about 10:1 to 0.1:1 and is preferably between about 5:1 to 0.25:1.
The reaction of the present invention will proceed at temperatures of from about 125C to 250C.
It is generally preferred to operate the process at temperatures of from about 175C to 225C to obtain a convenient rate of reaction. The reaction temperature will depend on the particular N-substituted carbamic acid ester being produced and should be below the temperature at which significant decomposition of the product ester might occur.
The process of the present invention is generally carried out at atmospheric pressure, although higher S~79 pressures of up to 50 atmospheres may be used and especially at the higher reaction temperatures or when the reaction temperature is above the boiling point of the alcohol and/or reactant amine. Subatmospheric pressures may be employed, if desired.
Ammonia resulting from the reaction must be removed during the course of the reaction, otherwise reduced yields of product carbamate are obtained. When the reaction is carried out at one atmosphere the ammonia is simply allowed to escape from the reaction vessel. In reactions where elevated pressures are employed provisions must be made to remove ammonia. A simple, convenient method is to strip the ammonia from the reactor with a dry inert gas, such as nitrogen or carbon dioxide and/or with the resulting alcohol vapor provided the alcohol employed is volatile at the reaction temperature. When the alcohol vapor is used to strip or aid in stripping the ammonia from the reactor, additional or makeup alcohol can be added to the reactor at a rate to compensate for the vapor loss.
The reaction time is generally dependent on the N-monosubstituted carbamate being produced, the reaction temperature and the catalyst employed, if any, and will vary depending on whether the process if continuous or batch but will generally range between about one to several hours.
The following Examples are provided to illustrate the invention in accordance with the principles of this invention, but are not to be construed as limiting the invention in any way except as indicated by the appended s~9 claims.
In the Examples which follow, the reactions were run in a 300 ml stainless steel stirred autoclave. The amine, unsubstituted carbamic acid ester and alcohol, along with tertiary amine catalyst and co-solvent, if any, are charged to the reactor which is then flushed with nitrogen and the reactor heated to the desired reaction temperature for a specified time period. During the reaction vaporized alcohol and product ammonia are stripped from the reactor with or without the aid of an inert gas. Makeup alcohol is pumped into the reactor at a rate closely approximating the alcohol removed. At the end of the reaction time, the autoclave is cooled to ambient temperature and the contents combined with the stripped alcohol which was collected in a dry ice cooled trap and the total mixture analyzed by liquid chromatog-raphy (LC) for conversion of amine and unsubstituted carbamic acid ester and selectivities to N-monosubstituted carbamate. Amine and the unsubstituted carbamate conver-sions were calculated on the basis of moles of the amine and carbamate consumed by the reaction. Product selec-tivities were based on the moles of amine or unsubstituted carbamate consumed in preparing the N-monosubstituted carbamate and by-products.
Example 1 _ 23.3 g aniline, 22.2 g ethyl carbamate and 220 ml of dry ethanol (200 proof) was charged to the autoclave which was flushed several times with nitrogen and heated to 200C for a period of 3 hours. During the reaction period ethanol and ammonia were stripped from the reactor 10 .
5'79 with nitrogen at an average of 1.7 ml of ethanol per minute. The ethanol vapor containing ammonia and a small amount of aniline was condensed in a dry ice cooled trap. Makeup ethanol was pumped into the autoclave at a rate closely approximating the amount stripped. After the reaction period, the autoclave was cooled and the contents along with the ethanol condensate analyzed.
LC analysis showed an aniline conversion of 34 percent and an ethylcarbamate conversion of 47.2 pe~cent with selectivities to ethylphenylcarbamate of 79 mole percent and 47.2 mole percent based on aniline and ethylcarbamateS
respectively.
Example 2 . . _ .
Example 1 was repeated using 100 ml ethanol and 100 ml benzene co-solvent. Analysis of the product and ethanol condensate showed an aniline conversion of 54 percent and an ethylcarbamate conversion of 65 percent.
Selectivities to ethylphenylcarbamate was 75 mole percent and 62 mole percent based on aniline and ethylcarbamate, respectively.
Example 3 Example 1 was repeated using 0.76 g 1,8-diaza-bicyclo[5.4.0]undec-7-ene as catalyst. Analysis showed an aniline conversion o~ 62.4 percent and an-ethyl-carbamate conversion of 84 percent with selectivities to ethylphenylcarbamate of 96.5 mole percent and 71 percent based on aniline and ethylcarbamate, respectively.
Example 4 Example 2 was repeated using 100 ml diphenyl-ether as a co-solvent, along with 0.4 mole of pyridine as 1~i579 catalyst. Analysis showed an aniline conversion of 55 percent and an ethylcarbamate of 66 percent with selec-tivities to ethylphenylcarbamate based on aniline and ethylcarbamate of 92 and 86 mole percent, respectively.
Examples 5 to 23 In Examples 5 to 23, which follow in Table form, the general procedure as hereinabove described was repeated using various amines, unsubstituted carbamic acid esters, alcohols, tertiary amine catalysts and conditions as shown in Table 1. The results are set forth in Table 2.
3o '~1 .~
oooooo ooooooooo o oU~o U~ooooo ooooooooo o o~
~1 ~ ~ N ~ ~ N ~ \I ~ N ~ ~ r-l N
~ g $ ~ o o o ~ ~ o o ~ o o U~
~} I I
t:4 00 a~ t` ~ r-i 00 ~ r` ~' 00 r-- 1` N Ir) 0 1-- 0 0 ~ ~ ~ ~ ~ ~ ~ 1 ~ ~ ~ ~ O ~ ~ ~ ~ ~
8 ~ ~ ~ 8 ~ ~ O ~ ~
U~
~ ~$ $$$$$$ $$$$$$$ $~ $~ ~ $$$
,~ ~
U~ C~ ~ U t~ V ~ V ~ U V C~
~ o~ ~ ~
...... ........ ~.~;........ .
1~46S~9 , ~
o o ~r ~
ui ~r a Y
13a .
'~
~ 5 u~ o ~ o ~ In o ~
~ ~ ~D ~ ~ ~ ~ ~0 ~ ~ a~ ~ ~ co 1` ~ ~` ~ ~D
~ ~ ~ a) ~ & ~ ~
N
~ o o~ ~ I~ ~ ~ In ~ ~ ~ ~ I` oo u~ I~ o o U~ u~
U.5 ~D ~ co ~ a~ ~ ~ ~ ~ ~ ~ ~ ~ co oo a~ ~ a~ co ~U ~ U ~ U ~ U ~U ~U ~ U
',~
~.~
U~
g) o ~ o ~ co ~ o :~
a) 14 .
1~46S79 U ~ ~
~ ~ 3 ~
o , , ~ ,` CO ~ o 14a.
Claims (22)
1. A process for the preparation of an N-monosubstituted carbamic acid ester which comprises reacting an unsubstituted carbamic acid ester having the formula NH2CO2R wherein R is a straight or branched chain alkyl group containing from 1 to 10 carbon atoms, with an aromatic primary amine having the formula R'(NH2)n wherein R' is a substituted or unsubstituted aryl or aralkyl group containing one or more benzenoid rings which may be fused or joined by single valency bonds and n is an integer of 1 to 6, at a temperature in the range of from about 125°C to 250°C in the presence of a monohydric aliphatic alcohol having from 1 to 10 carbon atoms.
2. A process according to claim 1 wherein the unsubstituted carbamic acid ester is selected from the group consisting of methylcarbamate, ethylcarbamate, and octylcarbamate.
3. A process according to claim 2 wherein the unsubstituted carbamic acid ester is ethyl carbamate.
4. A process according to claim 1 wherein the aromatic primary amine is selected from the group con-sisting of aniline, toluene diamines and naphthylamines.
5. A process according to claim 4 wherein the aromatic primary amine is aniline.
15.
15.
6. A process according to claim 1 wherein the reactant aromatic primary amine to unsubstituted carbamic acid ester is employed at a molar ratio of from about 10:1 to .1:1.
7. A process according to claim 6 wherein the molar ratio employed is from about 5:1 to .25:1.
8. A process according to claim 1 wherein the alcohol is employed at a molar ratio of from about .5:1.
to 15:1 based on the amine or unsubstituted carbamic acid reactant.
to 15:1 based on the amine or unsubstituted carbamic acid reactant.
9. A process according to claim 1 wherein the monohydric aliphatic alcohol is selected from the group consisting of methanol, ethanol, octanol and decanol.
10. A process according to claim 9 wherein the alcohol is ethanol.
11. A process according to claim 9 wherein the alcohol is methanol.
12. A process according to claim 1 wherein the process is carried out in the presence of a catalytic amount of from about .01 to 30 mole percent based on the aromatic primary amine employed of a tertiary amine which may be an aliphatic, cycloaliphatic, araliphatic, or aromatic amine containing from 1 to 18 carbon atoms.
13. A process according to claim 12 wherein the tertiary amine is employed in a catalytic amount of from .1 to 20 mole percent of the aromatic primary amine employed.
16.
16.
14. A process according to claim 12 wherein the tertiary amine is selected from the group consisting of triethylamine, tri-n-propylamine, tri-n-octylamine, pyridine, 1,5-diazabicyclo[4.3.0]non-5-ene and 1,8-diazabicyclo[5.4.0]undec-7-ene.
15. A process according to claim 14 wherein the tertiary amine is triethylamine.
16. A process according to claim 14 wherein the tertiary amine is pyridine.
17. A process according to claim 14 wherein the tertiary amine is 1,8-diazabicyclo[5.4.0]undec-7-ene.
18. A process according to claim 1 wherein the reaction temperature is in the range of from about 175°C to 225°C.
19. A process according to claim 1 wherein the reaction is carried out under a pressure of from 1 to 50 atmospheres.
20. A process according to claim 1 wherein the reaction is carried out in the presence of an inert solvent in addition to the alcohol.
21. A process for the preparation of ethyl-phenylcarbamate which comprises reacting ethylcarbamate with aniline at a temperature of from about 175°C to 225°C at a molar ratio of aniline to ethylcarbamate in the range of from 5:1 to .25:1 in the presence of ethyl alcohol and a catalytic amount of from 0.1 to 20 mole percent triethylamine.
17.
17.
22. A process according to claim 21 wherein the reaction is carried out in the presence of an inert solvent.
18.
18.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/135,946 US4381403A (en) | 1980-03-31 | 1980-03-31 | Process for the preparation of N-monosubstituted carbamic acid esters |
US135,946 | 1980-03-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1146579A true CA1146579A (en) | 1983-05-17 |
Family
ID=22470506
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000367769A Expired CA1146579A (en) | 1980-03-31 | 1980-12-31 | Process for the preparation of n-monosubstituted carbamic acid esters |
Country Status (9)
Country | Link |
---|---|
US (1) | US4381403A (en) |
JP (1) | JPS56145265A (en) |
BE (1) | BE888190A (en) |
CA (1) | CA1146579A (en) |
DE (1) | DE3112568A1 (en) |
FR (1) | FR2479209A1 (en) |
GB (1) | GB2072663A (en) |
IT (1) | IT1170727B (en) |
NL (1) | NL8100274A (en) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5182296A (en) * | 1989-10-26 | 1993-01-26 | Tanabe Seiyaky Co., Ltd. | Naphthyloxazolidone derivatives |
US5750604A (en) * | 1996-06-28 | 1998-05-12 | Tektronix, Inc. | Phase change ink formulation using a urethane isocyanate-derived resin |
US5782966A (en) | 1996-06-28 | 1998-07-21 | Tektronix, Inc. | Isocyanate-derived materials for use in phase change ink jet inks |
US6028138A (en) * | 1996-06-28 | 2000-02-22 | Tektronix, Inc. | Phase change ink formulation using urethane isocyanate-derived resins, a polyethylene wax and toughening agent |
US6018005A (en) * | 1996-06-28 | 2000-01-25 | Tektronix, Inc. | Phase change ink formulation using urethane isocyanate-derived resins and a polyethylene wax |
US5994453A (en) | 1996-06-28 | 1999-11-30 | Tektronix, Inc. | Phase change ink formulation containing a combination of a urethane resin, a mixed urethane/urea resin, a mono-amide and a polyethylene wax |
US5827918A (en) * | 1996-06-28 | 1998-10-27 | Tektronix, Inc. | Phase change ink formulation using urea and urethane isocyanate-derived resins |
US6180692B1 (en) | 1996-06-28 | 2001-01-30 | Xerox Corporation | Phase change ink formulation with organoleptic maskant additive |
US6730150B1 (en) * | 1996-06-28 | 2004-05-04 | Xerox Corporation | Phase change ink formulation containing a combination of a urethane resin, a mixed urethane/urearesin, a mono-amide and a polyethylene wax |
US6235094B1 (en) | 1996-06-28 | 2001-05-22 | Xerox Corporation | Phase change ink formulations, colorant formulations, and methods of forming colorants |
US6048925A (en) * | 1996-06-28 | 2000-04-11 | Xerox Corporation | Urethane isocyanate-derived resins for use in a phase change ink formulation |
US5783658A (en) * | 1996-06-28 | 1998-07-21 | Tektronix, Inc. | Phase change ink formulation using a urethane isocyanate-derived resin and a urethane isocyanate-derived wax |
US5830942A (en) * | 1996-06-28 | 1998-11-03 | Tektronix, Inc. | Phase change ink formulation using a urethane and urethane/urea isocyanate-derived resins |
US5919839A (en) * | 1996-06-28 | 1999-07-06 | Tektronix, Inc. | Phase change ink formulation using an isocyanate-derived wax and a clear ink carrier base |
US6015847A (en) * | 1998-02-13 | 2000-01-18 | Tektronix, Inc. | Magenta phase change ink formulation containing organic sulfonic acid |
US6309453B1 (en) | 1999-09-20 | 2001-10-30 | Xerox Corporation | Colorless compounds, solid inks, and printing methods |
US6395811B1 (en) | 1999-11-11 | 2002-05-28 | 3D Systems, Inc. | Phase change solid imaging material |
US6133353A (en) * | 1999-11-11 | 2000-10-17 | 3D Systems, Inc. | Phase change solid imaging material |
JP3644501B2 (en) | 2001-12-11 | 2005-04-27 | ソニー株式会社 | Recording / playback device |
CN101891651B (en) | 2009-05-19 | 2014-03-12 | 拜耳材料科技(中国)有限公司 | Catalyst used in preparation of N-substituted carbamate and preparation method and application thereof |
US8980406B2 (en) | 2012-08-28 | 2015-03-17 | 3D Systems, Inc. | Color stable inks and applications thereof |
US9657186B2 (en) | 2012-09-13 | 2017-05-23 | 3D Systems, Inc. | Opaque inks and applications thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2409712A (en) * | 1944-02-03 | 1946-10-22 | Du Pont | Chemical process and products |
US2943108A (en) * | 1955-01-21 | 1960-06-28 | Hooker Chemical Corp | Manufacture of carbamates from amides |
US2806051A (en) * | 1955-11-01 | 1957-09-10 | Goodrich Co B F | Method for preparing urethanes by reacting urea, amines and an alcohol |
US4375000A (en) * | 1979-04-30 | 1983-02-22 | Basf Aktiengesellschaft | Process for the preparation of an aryl mono-, di-, and/or polyurethane |
-
1980
- 1980-03-31 US US06/135,946 patent/US4381403A/en not_active Expired - Lifetime
- 1980-12-31 CA CA000367769A patent/CA1146579A/en not_active Expired
-
1981
- 1981-01-21 NL NL8100274A patent/NL8100274A/en not_active Application Discontinuation
- 1981-02-17 IT IT47819/81A patent/IT1170727B/en active
- 1981-03-09 GB GB8107352A patent/GB2072663A/en not_active Withdrawn
- 1981-03-13 JP JP3643081A patent/JPS56145265A/en active Pending
- 1981-03-24 FR FR8105825A patent/FR2479209A1/en active Granted
- 1981-03-30 BE BE0/204307A patent/BE888190A/en not_active IP Right Cessation
- 1981-03-30 DE DE19813112568 patent/DE3112568A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
FR2479209A1 (en) | 1981-10-02 |
NL8100274A (en) | 1981-11-02 |
IT8147819A0 (en) | 1981-02-17 |
IT1170727B (en) | 1987-06-03 |
FR2479209B1 (en) | 1985-01-11 |
US4381403A (en) | 1983-04-26 |
JPS56145265A (en) | 1981-11-11 |
DE3112568A1 (en) | 1982-01-28 |
GB2072663A (en) | 1981-10-07 |
BE888190A (en) | 1981-09-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1146579A (en) | Process for the preparation of n-monosubstituted carbamic acid esters | |
US4501915A (en) | Preparation of N-alkyl-monosubstituted carbamates | |
DE69602231T2 (en) | Process for the production of aromatic carbamates | |
US3992430A (en) | Process for preparing aromatic isocyanates | |
US4140716A (en) | Process for making an amide of formic acid and forming nitrodiarylamine therefrom | |
CA1155866A (en) | Preparation of n-monosubstituted carbamates | |
US5463109A (en) | Process for preparing carbamates | |
EP0919531B1 (en) | Process for the oxidation of aromatic compounds to hydroxyaromatic compounds | |
US4336402A (en) | Process for the preparation of N-alkyl-monosubstituted carbamic acid esters | |
CA1163650A (en) | Preparation of monoalkyl ethers of hydroxyphenols | |
KR100746846B1 (en) | Continuous process for the synthesis of aromatic urethanes | |
EP1065198B1 (en) | Process for the production of Malononitrile | |
US4172948A (en) | Preparation of diphenylmethane mono and dicarbamates and polymethylene polyphenyl carbamates | |
US5072024A (en) | Synthesis of N-substituted amides by condensation of nitriles with certain organic hydroxyl compounds | |
US4597911A (en) | Production of amino aliphatic and cycloaliphatic hydrogen sulfates | |
JPH0678304B2 (en) | Method for producing N-alkyl substituted lactam | |
WO2001047870A2 (en) | Process for the production of aromatic polycarbamates | |
KR860001548B1 (en) | Process for the preparation of substituted asymmetric ureas | |
GB1564023A (en) | Process for producing alkoxyanilines | |
US3941844A (en) | Continuous manufacture of N-alkylated arylamines | |
EP0635466A1 (en) | Decarboxylation process | |
US3979455A (en) | Preparation of dioxyimino-cycloalkanones and related intermediates | |
US5360601A (en) | Process for the preparation of isocyanic acid by the decomposition of N,N-disubstituted ureas | |
US4487952A (en) | Preparing carbamic acid esters | |
US4222959A (en) | Process for the preparation of aromatic formamides |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKEX | Expiry | ||
MKEX | Expiry |
Effective date: 20000517 |